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College of Materials Science and Engineering, National Engineering Research Center for Magnesium Alloys, Chongqing University, Chongqing 400044, China
Chongqing Academy of Science and Technology, Chongqing 401123, China
c
No. 59 Institute of China Ordnance Industry, Chongqing 400039, China
b
a r t i c l e
i n f o
Article history:
Received 24 July 2014
Received in revised form 2 September 2014
Accepted 7 September 2014
Available online 16 September 2014
Keywords:
Magnesium
Intermetallic compounds
Diffusion
Substitution
Kinetics
a b s t r a c t
The formation of AlCe intermetallic compounds (IMCs) during interdiffusion of MgAl/MgCe diffusion
couples prepared by solidliquid contact method was investigated at 623 K, 648 K and 673 K for 24 h,
48 h and 72 h, respectively. During the whole diffusion process, Al was the dominant diffusing species,
and it substituted for Mg of the MgCe substrate. Five AlCe IMCs of Al4Ce, Al11Ce3, Al3Ce, Al2Ce and AlCe
were formed via the reaction of Al and Ce. The formation of Al4Ce as the rst kind of IMC was rationalized
on the basis of an effective Gibbs free energy model. The activation energy for the growth of the total diffusion reaction layer was 36.6 kJ/mol.
2014 Published by Elsevier B.V.
1. Introduction
As the lightest metal structural materials, magnesium alloys
have high specic strength, excellent castability, and easy recyclability [1,2]. The current commercial use of magnesium alloys is
mainly focused on the MgAl-based alloys [3], as Al improves the
castability and mechanical properties at room temperature [4].
However, the application of commercially available MgAl based
alloys is limited to room or near room-temperature applications
because of their inferior creep resistance and lower strength at elevated temperatures [5]. The addition of cerium (Ce) is one of the
effective methods to optimize the microstructure and improve elevated temperature mechanical properties of MgAl alloys, due to
the formation of relatively thermally stable AlCe intermetallic
compounds (IMCs) [6].
The AlCe IMCs have attracted special attentions in recent
years. Many investigations of IMCs have been done when Ce is
added to MgAl alloys. For example, the morphologies of AlCe
IMCs in MgAlRE alloys are reported [7,8]. Al11Ce3 and Al3Ce
are acicular-like shaped and Al2Ce is quadrate-like shaped. The
thermal stability of Al11Ce3 and Al2Ce is investigated in
412
Fig. 1. Optical micrographs of the diffusion reaction layers for the diffusion couples
annealed at (a) 623 K, (b) 648 K, and (c) 673 K for 72 h.
Fig. 2. X-ray diffraction patterns of the reaction products after annealed at 673 K
for 72 h.
413
Fig. 3. SEM images of the diffusion reaction layers for the diffusion couples annealed at 673 K for (a) 24 h, (b) 48 h, (c) 72 h, and high magnication images of (d) the region 1,
(e) the region 2, (f) the region 3.
concentration of Al lower than the substrate of MgAl, and it presents a distribution of gradient decrease distribution showed Fig. 4.
Fig. 3(d)(f) is high magnication images of the regions 13,
respectively. For layers II and III, they are mainly composed of particle-like intermetallics, but the macro morphology is different. In
the layer IV, there are a lot of acicular-like intermetallics, which are
grown along the diffusion direction. Besides, a few quadrate-like
intermetallics particles can be found by careful BSE observations
nearby the MgCe substrate. While the EDS results taken from
the testing positions denoted in Fig. 3(d)(f) are summarized in
Table 1. Nevertheless, AlCe is not detected in BSE micrograph, even
after careful examination along the interface by using BSE at high
magnication. The probable reason is that the AlCe phase is too
small to be resolved by the used characterization techniques.
Fig. 4 shows the analysis of the EDS line scan across the diffusion couple in the sample is annealed at 673 K for 72 h, shown in
Fig. 4. Composition prole along the line scan shown in Fig. 3(c).
414
Table 1
EDS results taken from different positions of the diffusion layers as denoted in Fig. 3.
Zone
Mg (at.%)
Al (at.%)
Ce (at.%)
Al/Ce ratio
Phase
A
B
C
D
E
F
68.61
73.82
67.18
63.97
75.99
94.93
25.57
21.10
25.98
27.82
15.90
5.07
5.82
5.08
6.84
8.21
8.11
0
4.39
4.15
3.79
3.38
1.96
Al4Ce
Al4Ce
Al11Ce3
Al3Ce
Al2Ce
Solid solution
Fig. 3(c). The line scan contains data for 20 points. The concentration prole of Mg is a slight uctuation in layers II and III, but it is
increased in layers I and IV. The distribution of Al is decreased
gradually in layers I and IV, while the Al content remains to be a
constant from layer II to layer III. The concentration prole of Ce
is almost at in all zones. Because of the higher Al content in the
MgAl substrate and the higher Mg content in the MgCe substrate, Al atoms incline to diffuse to MgCe substrate and Mg
atoms to MgAl substrate. The concentration proles show that
the substitution of Mg is taken place by Al, and AlCe IMCs are
formed by AlCe reaction, along with their diffusion direction. It
can be concluded that the total diffusion reaction layers located
in the MgCe substrate, which is in good agreement with optical
micrographs in Fig. 1. This suggests that Al is the dominant diffusing species during the diffusion process, which may be related that
the diffusion of Al is faster than that of Ce in Mg. Al has a lower
melting point (933 K) than Ce (1072 K), and it may require less
activation energy for Al to migrate. In addition, the atomic radius
of Al (143 pm) is smaller than Ce (185 pm) which can allow Al to
move easily than Ce in Mg.
Fig. 5 shows the MgAlCe calculated isothermal section at
673 K [17], where the points are the line scan of the diffusion
couple annealed at 673 K for 72 h, and mainly located in
Al11Ce3 + (Mg), Al11Ce3 + Al3Ce + (Mg), Al3Ce + Al2Ce + (Mg) and
Al2Ce + (Mg) phase elds. The diffusion path of the diffusion couple
is along the line with points. Nevertheless, no related data for Al4Ce
in ternary phase diagram of the MgAlCe system was reported, so
it cannot nd the corresponding region in the phase diagram. AlCe
cannot be determined in the phase elds of the diffusion path
through. From the analysis of the MgAlCe calculated isothermal
Fig. 6. (a) Formation enthalpies of the MgAl, MgCe and AlCe binary systems and
(b) Gibbs free energies of the formation of different AlCe IMCs as the function of
temperature.
GS C A GA C B GB DHSmix T DSSmix
415
where CA and CB are the mole fractions of A and B elements, respectively. GA and GB are the Gibbs free energy of the pure element A and
B, respectively. DHSmix is the enthalpy change during intermixing,
DSSmix RC A ln C A C B lnC B is the ideal entropy of intermixing,
and T is the temperature. The enthalpy change of a solid solution
phase can be determined by the semi-experimental Miedemas
model:
where the three terms are the chemical, elastic, and structural contributions, respectively. The chemical term DHC can be expressed
by:
S
Sol
DHC C A C B C SB DHSol
A in B C A DH B in A
S
where DHSol
A in B is the solution enthalpy of A in B, C B is the degree to
which A atoms are in contact with B atoms. The elastic term for a
solid solution phase is often calculated by:
DHE C A C B C B DHeA
in B
C A DHeB
in A
DHeB in A
where
is the elastic contribution to the heat of solution of B
in A in the solid solution phase. DHS is different from zero only for
transition metaltransition metal alloys [22]. For the AlCe solutions, Al a main group metal and Ce is a transition metal, so the
structure contribution DHS 0.
Based on the equations described above, the values of Gibbs free
energies are calculated in the temperature range 623673 K and
the results obtained are shown in Fig. 6(b). The parameter values
for calculations are taken from the literature [23]. It can be found
in this gure that in this temperature range, the Gibbs free energy
of Al4Ce is more negative than the other phases, resulting in the
preferential formation of Al4Ce at the interface, and Al11Ce3 is the
second, and the sequence of following IMCs is Al3Ce, Al2Ce and
AlCe, which are in good agreement with the experimental
observations.
Fig. 7. (a) Relationship between the thickness of the diffusion reaction layers and
the square root of treatment times for all the diffusion couples and (b) an Arrhenius
plot of the diffusion reaction layers growth.
K K 0 exp
Q 0
RT
Q0
RT
or
ln K ln K 0
d Kt1=2
416
Acknowledgments
The authors are grateful for the nancial supports from Chongqing
Science and Technology Commission (CSTC2013jcyjC60001,
CSTC2012JJJQ50001, cstc2012ggB50003), National Natural Science
Foundation of China (51171212), and The National Science and
Technology Program of China (2013DFA71070, 2013CB632200),
and the Fundamental Research Funds for the Central Universities
(CDJZR13138801, CDJXS12131106).
References
[1]
[2]
[3]
[4]
[5] J. Zhang, J. Wang, X. Qiu, D. Zhang, Z. Tian, X. Niu, D. Tang, J. Meng, J. Alloys
Comp. 464 (2008) 556564.
[6] T.L. Chia, M. Easton, S.M. Zhu, M. Gibson, N. Birbilis, J. Nie, Intermetallics 17
(2009) 481490.
[7] X. Tian, L. Wang, J. Wang, Y. Liu, J. An, Z. Cao, J. Alloys Comp. 465 (2008) 412
416.
[8] T. Rzychon, A. Kiebus, J. Cwajna, J. Mizera, Mater. Charact. 60 (2009) 1107
1113.
[9] J. Zhang, Z. Leng, S. Liu, M. Zhang, J. Meng, R. Wu, J. Alloys Comp. 509 (2011)
L187L193.
[10] S. Brennan, K. Bermudez, N.S. Kulkarni, Y. Sohn, Metall. Mater. Trans. A 43
(2012) 40434052.
[11] S.K. Das, Y.M. Kim, T.K. Ha, R. Gauvin, I.H. Jung, Metall. Mater. Trans. A 44
(2013) 25392547.
[12] Y.B. Kang, A.D. Pelton, P. Chartrand, C.D. Fuerst, Calphad 32 (2008) 413422.
[13] L. Jin, Y.B. Kang, P. Chartrand, C.D. Fuerst, Calphad 35 (2011) 3041.
[14] S. Brennan, A.P. Warren, K.R. Coffey, N. Kulkarni, P. Todd, M. Kilmov, Y. Sohn, J.
Phase Equilib. Diffus. 33 (2012) 121125.
[15] X. Zhang, D. Kevorkov, M.O. Pekguleryuz, J. Alloys Comp. 501 (2010) 366370.
[16] L. Jin, D. Kevorkov, M. Medraj, P. Chartrand, J. Chem. Thermodyn. 58 (2013)
166195.
[17] V. Raghavan, J. Phase Equilib. Diffus. 28 (2007) 453455.
[18] A.R. Miedema, P.F. Dechatel, F.R. Deboer, Physica B 100 (1980) 128.
[19] G. Borzone, G. Cacciamani, R. Ferro, Metall. Mater. Trans. A 22 (1991) 2119
2123.
[20] G. Cacciamani, R. Ferro, Calphad 25 (2001) 583597.
[21] Y. Guo, G. Liu, H. Jin, Z. Shi, G. Qiao, J. Mater. Sci. 46 (2010) 24672473.
[22] H. Bakker, G. Zhou, H. Yang, Prog. Mater. Sci. 39 (1995) 159241.
[23] A.T. Dinsdale, Calphad 15 (1991) 317425.
[24] J. Hirmke, M.X. Zhang, D.H. St John, Metall. Mater. Trans. A 43 (2012) 1621
1628.